Process for preparing epoxy compounds and resulting products



United States Patent 3,336,241 PROCESS FOR PREPARING EPOXY COMPOUNDS ANDRESULTING PRODUCTS Edward C. Shokal, Walnut Creek, Calif., assignor toShell Oil Company, New York, N.Y., a corporation of Delaware No Drawing.Filed Nov. 12, 1963, Ser. No. 323,084

22 Claims. (Cl. 2602) ABSTRACT OF THE DISCLOSURE A process is disclosedfor the treatment of compounds having at least one Vic-epoxy group andcarbon-to-carbon double bond unsaturation with hydrogen in the presenceof a catalyst consisting of rhodium or ruthenium supported on an inertcarrier, at a temperature below 50 C. The carbon-to-carbon unsaturationis partially or completely saturated without materially affecting thevicepoxy group. Lists of compounds to be hydrogenated as Well as listsof the resulting products, and reaction conditions such as temperature,amount of catalyst and presence of solvents are disclosed. The resultinghydrogenated products are shown to be curable with conventional epoxyresin curing agents and are disclosed as being useful for preparingadhesives, laminates, castings and moldings.

This invention relates to a new process for preparing epoxy compounds.More particularly, the invention relates to a new process for preparingsaturated or substantially saturated epoxy compounds from thecorresponding unsaturated epoxy compound, to the resulting new epoxycompounds and to their utilization.

Specifically, the invention provides a new and highly elficient processfor converting compounds possessing carbon-to-carbon unsaturation and atleast one Vic-epoxy group to corresponding compounds which are partiallyor completely saturated Without materially affecting the epoxy group.This new process comprises treating the unsaturated epoxy compound withhydrogen in the presence of a finely divided solid catalyst containing ametal of the group consisting of rhodium :and ruthenium preferablysupported on an inert carrier, such as carbon, at a temperature below 50C. As a special embodiment, the invention provides a process forpreparing saturated or substantially saturated cycloaliphatic orheterocyclic epoxy compounds, such as for example, glycidyl ethers ofcycloalphatic alcohols, which comprises treating the correspondingaromatic or unsaturated heterocyclic epoxy compound with hydrogen in thepresence of finely divided rhodium or ruthenium metal supported on afinely divided charcoal or alpha alumina carrier at a temperature above50 C.

The invention further provides new saturated or substantially saturatedepoxy compounds and polymers many of which have never been availableheretofore because of the difficulty of their manufacture, andparticularly the saturated cycloaliphatic or heterocyclic epoxycompounds and polymers.

The invention further provides new and particularly useful insoluble andinfusible cured products obtained by reacting the above-describedsaturated or substantially saturated epoxy compounds with materials,such as amines, polycarboxylic acids or anhydrides, polymercaptans,hydrazides, metal salts, boron trifluoride and complexes therewith, andthe like.

As a special feature the invention provides hydrogenated epoxy ethers ofpolyhydric phenols which can be cured to give products havingsurprisingly good resistance to chalking and discoloration caused byexposure to outdoor conditions.

aliphatic or cycloaliphatic epoxy compounds. The aliphatic andcycloaliphatic compounds are not as reactive toward materials, such asepichlorohydrin, and several steps are required to obtained the desiredaliphatic or cycloaliphatic epoxy ethers. In some cases, it is almostimpossible to prepare the epoxy compound from the desired aliphatic orcycloaliphatic compound.

It is an object of the invention, therefore, to provide a new processfor preparing epoxy compounds. It is a further object to provide a newand highly efficient process for preparing saturated or substantiallysaturated epoxy-substituted compounds. It is a further object to providea new technique for preparing epoxy substituted cycloaliphatic orheterocyclic compounds from the corresponding epoxy-substituted aromaticor unsaturated heterocyclic compound. It is a further object to providea new process for converting epoxy aromatic compounds to epoxycycloaliphatic compounds without materially affecting the epoxy group.It is a further object to provide a new group of epoxy compounds whichfind wide application in industry. It is a further object to provide aprocess for making epoxy compounds which have improved compatibilitywith hydrocarbon polymers and resins, paraflinic solvents and the like.It is a further object to provide new hydrogenated epoxy ethers ofpolyhydric phenol which give cured products having excellent resistanceto outdoor conditions. These and other objects of the invention will beapparent from the following detailed description thereof.

It has now been discovered that these and other objects may beaccomplished by the process of the invention which comprises treatingthe compounds possessing carbon-to-carbon unsaturation and at least onevie-epoxy group with hydrogen in the presence of a finely-dividedcatalyst containing a metal of the group consisting of rhodium andruthenium preferably supported on an inert carrier, such as charcoal oralpha-alumina at a temperaphatic compound, such as the glycidyl ether of2,2-bis(4- hydroxycyclohexyl)propane. The process is particularly suitedfor use in the conversion of compounds having aromatic rings as suchrings can be completely or partially converted to the cycloaliphaticring without affecting the epoxy groups. It has been further discoveredthat the hydrogenated products of the invention and particularly theepoxy ethers of polyhydric phenols, can be cured to form products havingoutstanding resistance to discoloration and chalking by exposure tooutdoor conditions. In this regard they are far superior to theunhydrogenated epoxy compounds.

That the above-described results could be accomplished by such a processwas quite surprising in view of the fact that it was expected that theepoxy groups were very sensitive to hydrogenation and that they would bemore easily attacked than the aromatic rings. Further, it was expectedthat catalysts, such as rhodium and ruthenium, were very activehydrogenation catalysts and possessed no selective characteristics asdescribed above.

The compounds that may be converted by the process of the inventioninclude those organic compounds possessing carbon-to-carbon unsaturationand at least one vicepoxy group. These materials may be monomer orpolymeric, and may be substituted with other groups, such as ether,ester, hydroxyl, mercaptan, halogen, carboxyl and the like groups. Thecompounds may be aliphatic, cycloaliphatic, aromatic or heterocyclic butas noted above, the superior properties are more in evidence whenutilizing an aromatic or unsaturated heterocyclic compound. The cycliccompounds may be monoor polynuclear and may have single or fuzed rings.The epoxy group may be terminal, i.e.,

or internal, i.e.,

and may have other substituents on the carbons other than hydrogen suchas OHC- The epoxy group may also be a part of a ring structure, such assuch as in Examples of these compounds include, among others,epoxy-containing aromatic ethers, such as, for example, phenyl glycidylether, 3,4-epoxybutyl phenyl ether, diglycidyl ether of resorcinol,diglycidyl ether of 2,2-bis(4- hydroxyphenyl) propane, diglycidyl etherof 2,2-bis(4- hydroxyphenyl)butane, diglycidyl ether of novolac resinsobtained by condensing phenol with formaldehyde, gly- OR O wherein n is1 to 25. Preferred reactants are the glycidyl ethers of polyhydricphenols containing no more than 30 carbon atoms. Coming under specialconsideration are the glycidyl ethers of the dihydric phenols of theformula R R R R R R R R wherein R may be hydrogen, alkyl groups (i.e., 1to 8 carbon atoms), -OR groups wherein R is alkyl, COOH, -COOR wherein Ris an alkyl group.

Other examples include those having the epoxyalkyl group attacheddirectly to aromatic ring or rings, such as, for example,glycidylbenzene, 1,4-diglycidylbenzene, 1,3,5 triglycidylbenzene,di(epoxyethyl)benzene, 2,3- epoxybutylbenzene, glycidyl naphthalene,2,2-bis(3-glycidyl-4-hydroxyphenyl)propane, butyl glycidylbenzoate,ester of ethylene of glycol and glycidylbenzoate, glycidyl aniline,glycidylphenyl allyl ether, glycidyltoluene diisocyanate, amide ofdiethylene amine and glycidylphthalic acid, and the like.

Examples of other materials include those which have the epoxyalkylgroup attached to the aromatic ring or rings through nitrogen such asN,N-diglycidyl aniline, N,N'-diglycidyl methylene dianiline,N,N'-diglycidyl 2,2- bis(4-aminophenyl)propane and the like.

Other examples include compounds wherein the epoxyalkyl group isattached to the aromatic ring or rings through an ester linkage.Examples of such include, among others, diglycidyl phthalate, diglycidylisophthalate, glycidyl benzoate, epoxidized dicrotyl phthalate,epoxidized dimethallyl phthalate, glycidyl ester of2,2-di(hydroxypheny.l)-S-pentanoic acid, glycidyl allyl phthalate,glycidyl ester of naphthoic acid, glycidyl pyromellitate, glycidyl esterof trimellitic acid, di(3,4- epoxybutyl) phthalate, di(2,3-epoxycyclohexyl) isophthalate, 3,4-epoxyhexyl benzoate, and thelike.

Still other examples include the homopolymers, copolymers, terpolymers,etc. of unsaturated monomers which contain both the epoxy group andaromatic ring or rings. Illustrative examples of these include, amongothers, polymers of glycidyl ether of vinyl phenol, glycidyl ether ofallylphenol, epoxycyclohexyl ether of allyl phenol,epoxycyclohexylmethyl ether of vinyl phenol, acrylic acid ester ofglycidyloxy-substituted phenol, methacrylic acid ester ofepoxycyclohexyloxy-substituted phenol glycidyl allyl phthalate, glycidylvinyl isophthalate and epoxy cyclohexyl allyl trimellitate. Thesepolymers include the homopolymers as well as the mixed polymers withdissimilar monomers containing ethylenic linkages which may be any ofthe above as well as monomers such as, for example, styrene, vinylchloride, acrylonitrile, vinyl acetate, methacrylonitrile, acrylic acid,methacrylic acid, ethyl acrylate, butyl methacrylate, diallyl phthalate,vinyl methallyl phthalate, divinyl adipate, chloroallyl acetate, vinylmethallyl pimelate, alpha-methylstyrene, butadiene, isoprene ethylene,propylene, isobutylene, vinylidene chloride, acrylamide, and the like,and mixtures thereof.

Other examples include those containing an epoxy group and anunsaturated heterocyclic ring, such as compounds having an epoxy groupand one or more furan, thiophene, pyrrole, pyrone, pyridine, indole,quinoline, isoquinoline, dihydropyran and the like rings. Specificexamples include, among others, glycidyl ester of3,4-dihydro-1,Z-pyrane-Z-carboxylate, 2,3-epoxycyclohexyl 3,4-dihydro-1,2-pyran-2-carboxylate, 3,4-epoxyhexyl3,4-dihydro-1,2-pyran-2-carboxylate, glycidyl2,3-dihydrothiophene-2carboxylate, glycidyl N-methyl 1,2,3,4-tetrahydropyridine-2-carboxylate, glycidyl N-methyl2,3-dihydropyrrole-2-carboxylate, 2,3-epoxycyclohexyl Z-furoate,glycidyl pyrrole-2-carboxylate, glycidyl 2,3-dihydrfuran-2- carboxylate,glycidyl ether of 3,4-dihydro-1,2-pyran-2-ol, glycidyl ether of2,3-dihydrothiophene-2-ol, 2,3-epoxycyclohexyl ether of2,3-dihydrofuran-2-ol, compounds wherein the glycidyl group is attacheddirect to the furan, thiophenepyrrole, pyrone, pyridine molecules andthe like. Also included within this group are the polymers of theabove-described monomers such as may be obtained by homopolymerizing orcopolymerizing the monomers or interpolymerizing them with otherunsaturated monomers, such as, for example, styrene, vinyl chloride,acrylonitrile, vinyl acetate, methacrylonitrile, acrylic acid, ethylacrylate, butyl methacrylate, diallyl phthalate, vinyl methallylphthalate, divinyl adipate, alpha-methylstyrene, butadiene, isoprene,ethylene, propylene, isobutylene, acrylamide and the like.

Still other examples include those materials, preferably of thepolymeric type, wherein the epoxy group and the aromatic or unsaturatedheterocyclic ring or rings do not appear in the same unit but do appearin the same molecule. Examples of these include, for instance,copolymers of allyl glycidyl ether and styrene, allyl glycidyl ether andalpha-methylstyrene, terpolymers of butadiene, allyl glycidyl ether andp-methylstyrene, copolymers of glycidyl acrylate and styrene,terpolymers of allyl alcohol, glycidyl acrylate and styrene, copolymersof glycidyl methacrylate and allyloxy ether of phenol, copolymers ofglycidyl cyclohexanecarboxylate and allyl ether of 2,2-bis(4-hydroxyphenyl)propane, terpolymer of vinyl acetate, allyl glycidylether and N-allyl aniline, terpolymer of allyl glycidyl ether, styreneand vinyl acetate and the like.

Still other examples include condensation polymers containing epoxidegroups as side or terminal groups and aromatic groups as part of themolecule. Phthalic (or iso or tere) acid condensations with glycols 0ramines with excess acid give products with carboxylic groups thatfurther react with epichlorohydrin to form glycidyl derivitives, hydroxybenzoic acid polyol or polyamine condensation products further reactedwith epichlorohydrin (glycols, glycerol, pentaerythritol, ethylenediamine, di-

ethylene triamine are examples of polyols and amines).

Less preferred materials to be used in the process of the inventioninclude those containing epoxy groups and unsaturation of the aliphaticor cycloaliphatic type. Examples of these include, among others,butadiene monoepoxide, vinyl cyclohexene monoepoxide, allyl glycidylether, cyclohexenyl glycidyl ether, copolymers of butadiene and allylglycidyl ether, copolymers of butadiene and glycidyl acrylate,copolymers of methylpentadiene and epoxycyclohexyl acrylate, copolymersof methylpentadiene and epoxycyclohexyl acrylate, copolymers ofcyclopentadiene and glycidyl methacrylate, partially epoxidizedpolybutadiene, partially epoxidized copolymers of butadiene and allylalcohol, partially epoxidized copolymers of butadiene and styrene,partially epoxidized terpolymers of butadiene, acrylonitrile andstyrene, and the like.

The process of the invention comprises treating the above-describedcompounds or polymers possessing the epoxy group and unsaturation withhydrogen in the presence of a finely-divided rhodium or rutheniumcatalyst supported on an inert carrier at a temperature below 6 150 C.The hydrogenation catalyst consists of rhodium or ruthenium metal or acompound of rhodium or ruthenium in a finely divided state e.g., 50 meshor less and preferably 800 1200 mesh. The surface area of the catalystas compared to that of a sphere will be large. The greater the area, themore efiicient the catalyst. The rhodium and ruthenium metal orcompounds can be used alone or supported by an inert carrier to increaseits surface area. By inert carrier is meant one that is nonreactive withepoxide compounds with or without the.

catalyst. Metal oxides of aluminum, zirconium, titanium, calcium,silicon, magnesium, tin, molybdenum, and iron are useful. Carbon andcarbides as silicon carbide, boron carbide, are useful as carriers.

Particularly preferred carriers are those of relatively low surfacearea, e.g., those having an area of less than 50 square meters per gram.Examples of these include alpha-alumina, oxides of zirconium, titaniumand mag nesium.

The amount of the catalyst to be employed may vary over a considerablerange. In general, the amount of the catalyst (metal) will vary fromabout .1% to about 10% by weight of the epoxy-containing compound.Preferred amounts of catalyst range from about .5 to about 5% by weight.

The temperature employed during the reaction will be below 100 C.Preferred temperatures range from ambient temperature to about 50 C.Temperatures above the 100 C. bring about a loss in epoxy group andshould not be employed if high epoxy values are desired.

The hydrogen pressure preferably employed varies from about 50 to 800p.s.i., although higher pressures such as those up to or over 2000p.s.i. may be employed. Particularly preferred pressures vary from about10 to 500 p.s.i.

The hydrogenation is preferably accomplished in an inert solvent, suchas dioxane, tetrahydrofuran, cyclohexane, isopropyl alcohol, ethers,mixed ether alcohols of polyols or mixtures of inert solvents, and thelike, and mixtures thereof. The amount of the solvent employedpreferably varies from 50 to 90%. However, with low viscosity systemsthe solvent can be reduced or completely eliminated.

In most cases, the hydrogen is rapidly absorbed under the conditions ofthe reaction and the reaction time is relatively short. In general,reaction times vary from about 1 hour to about 24 hours depending on theconditions and material being hydrogenated. The reaction can be stoppedat any time if only partial hydrogenation is desired as notedhereinafter.

The reaction may be stopped by conventional means, such as reducingtemperature, killing or removal of the catalyst, addition of aninhibitor and the like. The catalyst may be removed by filtration orcentrifugation and the solvents or diluents removed by distillation. Insome cases, it may be desirable to leave the solvent or diluent in themixture and use the combined mixture in the intended application.

The resulting products in purified form will vary in physical form fromfree flowing liquids to solids depending on the starting material. Inchemical structure, they will have the same structure as the startingmaterial with the exception that the carbon-to-carbon unsaturation willbe converted to a saturated carbon-to-carbon linkage in the desireddegree. For most applications, it is desired to effect a substantiallycomplete conversion of the unsaturated linkages to saturated linkages.However, in some cases, it may be desirable to effect only a partial,e.g., 20% to conversion of unsaturated linkages to the saturatedlinkages.

The products will also have substantially the same number of epoxygroups as the starting material and can be further reacted through theepoxy group to form a variety of different types of derivatives andpolymers. These epoxy compounds, for example, can be reacted withamines, thiols, H S, HCl, HBr, HI, acids and the like. The epoxycompounds which have more than one epoxy group may be reacted with epoxycuring agents to form hard insoluble infusible castings. The curingagents for the products include materials which are preferably acidic oralkaline. Examples of suitable curing agents include among others, thepolybasic acids, such as, for example, the di-, triand higher carboxylicacids as oxalic acid, phthalic acid, terephthalic acid, succinic acid,alkyl and alkenyl-substituted succinic acids, tartaric acid, andparticularly the polymerized unsaturated acids, such as, for example,those containing at least 10 carbon atoms, and preferably more than 14carbon atoms, as for instance dodecenedioic acid, 10,12-eicsadienedioicacid, teradecenoic acid, linoleic acid, linolenic acid, eleostearic acidand licannic acid. Particularly preferred acids are the trimerizedacids, obtained from the ethylenically unsaturated fatty acids asderived from semi-drying and drying oils, and particularly theconjugated fatty acids containing from 12 to 20 carbon atoms.

Other preferred curing agents include the amino-containing compounds,such as, for example, diethylene triamine, triethylene tetramine,dicyandiamide, melamine, pyridine, cyclohexylamine, benzyldimethylamine,benzylamine, diethylamine, triethanolamine, piperidine,tetramethylpiperazine, N,N-dibutyl 1,3-propane diamine,N,N-diethyl-1,3-propane diamine, 1,2-diamino-2-methyl propane,2,3-diamino-2 methylbutane, 2,3 diamino 2- methylpentane,2,4-diamino-2,6-dimethyloctane, dibutylamine, dioctylamine,dinonylamine, distearylamine, diallylamine, dicyclohexylamine,methylethylamine, ethylcyclohexylamine, pyrrolidine,2-methylpyrrolidine, tetrahydropyridine, 2-methylpiperidine,2,6-dimethylpiperidine, diaminopyridine, tetramethylpentane,metaphenylene diamine and the like, and soluble adducts of amines andpolyepoxides and their salts, such as described in US. 2,651,589 and US.2,640,037. Still other examples include the acetone soluble reactionproducts of polyamines and monoepoxides, the acetone soluble reactionproducts of polyamines with unsaturated nitriles, such as acrylonitrile,imidazoline compounds as obtained by reacting monocarboxylic acids withpolyamines, sulfur and/or phosphorous-containing polyamines as obtainedby reacting a mercaptan or phosphine containing active hydrogen with anepoxide halide to form a halohydrin, dehydrochlorinating and thenreacting the resulting product with a polyamine, soluble reactionproducts of polyamines with acrylates, and many other types of reactionproducts of the amines.

Still other curing agents that may be used include the polycarboxylicacid anhydrides, such as, for example, pyromellitic anhydride, phthalicanhydride, succinic acid anhydride, maleic acid anhydride, borontrifiuoride and complexes of boron trifiuoride with amines, ethers,phenols and the like, Friedel-Crafts metal salts, such as aluminumchloride, zinc chloride, and other salts, such as zinc fluoborate,magnesium perchlorate and zinc fluosilicate; inorganic acids and partialesters as phosphoric acid and partial esters thereof including n-butylorthophosphite, diethyl orthophosphate and hexaethyltetraphosphate andthe like.

Another type of curing agent to be employed includes the polyamidescontaining active amino and/or carboxyl groups, and preferably thosecontaining a plurality of amino hydrogen atoms. Examples of polybasicmaterials used in making these polyamides include, among others,1,10-decanedioic acid, 1,12-dodecanedienedioic acid, 1,20-eicosadienedioic acid, 1,14-tetradecanedioic acid, 1,18- octadecanedioicacid and dimerized and trimerized fatty acids as described above. Aminesused in making the polyamides include preferably the aliphatic andcycloaliphatic polyamines as ethylene diamine, diethylene triamine,triethylene tetramine, tetraethylene pentamine, 1,4-diaminobutane,1,3-diaminobutane, hexamethylene diamine, 3-(N-isopropylamino)propylamine and the like. Especially preferred polyamidesare those derived from the aliphatic polyamides containing no more than12 carbon atoms and polymeric fatty acids obtained by dimerizing and/ ortrimerizing ethylenically unsaturated fatty acids containing up to 25carbon atoms. These preferred polyamides have a viscosity between 10 and750 poises at 40 C., and preferably 20 to 250 poises at 40 C. Preferredpolyamides also have amine value of 50 to 450.

Still another group of curing agents are those based on melaminereaction products containing methylol substituents.

The amount of curing agent may vary considerably depending upon theparticular agent employed. For the alkalies or phenoxides, 1% to 4% isgenerally suitable With phosphoric acid and esters thereof, good resultsare obtained with 1 to 10% added. The tertiary amine compounds arepreferably used in amounts of about 1% to 15%. The acids, anhydrides,polyamides, polyamines, polymercaptans, etc., are preferably used in atleast 0.8 equivalent amounts, and preferably 0.8 to 1.5 equivalentamounts. An equivalent amount refers to that amount needed to give oneactive H (or anhydride group) per epoxy group.

The compositions of the invention may be prepared by a variety ofdifferent methods. All of the components may be mixed together in anyorder, or they may be mixed together in separate groups.

Solvents or diluents may also be added to make the composition morefluid or sprayable. Preferred solvents or diluents include those whichare volatile and escape from the polyepoxide composition before orduring cure such as, esters as ethyl acetate, butyl acetate, Cellosolveacetate (ethylene glycol monoacetate), methyl Cellosolve acetate(acetate ethylene glycol monomethyl ether), etc., ether alcohols, suchas methyl, ethyl or butyl ether of ethylene glycol or diethylene glycol;chlorinated hydrocarbons such as trichloropropane, chloroform, etc. Tosave expense, these active solvents may be used in admixture witharomatic hydrocarbons such as benzene, toluene, xylene, etc. and/oralcohols such as ethyl, isopropyl or n-butyl alcohol. Solvents whichremain in the cured compositions may also be used, such as diethylphthalate, dibutyl phthalate and the like, as well as cyanosubstitutedhydrocarbons, such as acetonitrile, propionitrile, adiponitrile,benzonitrile, and the like. It is also convenient to employ normallyliquid glycidyl compounds, such as glycidyl phenyl ether, glycidyl allylether, glycidyl acrylate, glycidyl cyclopentyl ether, diglycidyl ether,glycidyl ether of glycerol and the like, and mixtures thereof.

Other materials may also be added to the composition as desired. Thisincludes other types of polyepoxides such as described in US. 2,633,458.This also includes fillers, as sand, rocks, resin particles, graphite,asbestos, glass or metal oxide fillers and the like, plasticizers,stabilizers asphalts, tars, resins, insecticides, fungicides,stabilizers, antioxidants, pigments, stains, and the like.

The temperature employed in the cure Will vary depending chiefly on thetype of curing agent. The amino-containing curing agents generally cureat or near room temperature and no heat need be applied. The acids,anhydrides and melamine derivatives, on the other hand, are generallyused with heat, such as temperatures ranging from F. to about 400 F.Preferred temperatures range from about 200 F. to about 400 F. and morepreferably from about 250 F. to 350 F.

The compositions containing the polyepoxides and curing agents may beused for a variety of important applications. They may be used, forexample, as adhesives for metal, Wood, concrete, plaster and the like,and as surface coatings for various types of surfaces. The newcompositions may also be used in the preparation of laminates orresinous particles reinforced with fibrous textiles. They may also beused in the formation of castings and moldings and for the encapsulationof electrical equipment.

As noted above,.the new epoxy compounds, and particularly those derivedby hydrogenating epoxy ethers of polyhydric phenols, can be cured toform products having outstanding resistance to discoloration andchalking by outdoor conditions. As a result, the new products areparticularly suited for use as surface coatings, such as paints,lacquers, enamels and the like, and especially those intended foroutdoor use. In these applications, the new epoxy compounds arepreferably mixed with a curing agent such as amine or anhydride, asolvent or diluent, pigment, etc. and then the resulting mixture spreadout on the desired surface to dry. Heat may be applied to accelerate thecure.

The new polyepoxides may also be used to produce higher molecular weightproducts as by reaction with con trolled amounts of polyhydric phenols,such as Bisphenol-A, hydroquinone and the like. In this way, high moleweight products terminating either in epoxy groups or phenol groups canbe prepared.

To illustrate the manner in which the invention may be carried out, thefollowing examples are given. It is to be understood, however, that theexamples are for the purpose of illustration and that the invention isnot to be regarded as limited to any of the specific conditions orreactants recited therein. Unless otherwise indicated, parts describedin the examples are parts by weight. The polyethers referred to byletter are those in US. 2,633,458.

Example I 250 parts of dioxane purified by refluxing over caustic,fractionating in a N atm. and containing less than 5 ppm. was added to aglass hydrogenation bottle containing 25 parts (0.073 mole) of thediglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane. Four grams offinelydivided catalyst (10% rhodium or carbon) approximately 800-1200mesh, and after all the air was replaced with N and the N replaced withhydrogen, the hydrogen pressure was raised to 50 p.s.i.g. and shakingstarted and kept at room temperature.

After 22 hours of hydrogenation, 0.5 mole of hydrogen had been consumed.The catalyst was removed by filtration under N and the dioxane removedby vacuum distillation. The product, 20 g., remaining as bottoms was awater white liquid which analyzed as follows:

Product epoxy content 0.390 eq./100 g. Starting material epoxy content0.587 eq./ 100 g.

66.5 mole percent of the original epoxy groups were recovered unchanged.An infrared analysis of the undiluted product between NaCl plates showedno absorption at 6.2 microns showing that no aromatic components wereleft. The starting material has a strong absorption at 6.2 microns.

11% by weight of diethylene diamine added to a portion of this productconverted it into a hard tough infusible resin on standing overnight atroom temperature.

Example 11 The procedures and quantities of reagents in Example I wererepeated with the exception that the rhodium catalyst recovered fromExample I was used instead of a fresh batch.

After 10.5 hours of hydrogenation 0.41 mole of hydrogen was absorbed andcontinuing the hydrogenation for another 1% hours did not increase thehydrogen absorption. The product was recovered as described in ExampleI. It analyzed as follows: Epoxy content, 0.530 eq./100 g. I

91.3% of the original epoxy groups were recovered unchanged. Infraredanalysis of the undiluted product between NaCl plates showed noabsorption at 6.2 microns showing that no aromatic components were left.

By comparing Examples I and II and data below it becomes apparent thatthe selectivity of the catalyst improves with use. The active sites thathave the least selectivity are deactivated quite rapidly so thatsubsequent use of the catalyst gives a product with a greater epoxyretention. Epoxy retentions over have been obtained in some instances.

11% by Weight of diethylene diamine added to a portion of this productconverted it into a hard tough infusible resin on standing overnight atroom temperature.

In a similar manner the polyglycidyl ethers of a,a,a',a',a",a"-hexakis(hydroxyphenyl) 1,3,5-triethyl benzene, cc,a,a',a'-tetrakis(hydroxyphenyl)ethane andot,cc,oc',a'-tetl'akis(hydroxymethylphenyl)ethane can be hydrogenatedwith the catalyst.

Example 111 -phere, the N replaced with H and brought to p.s.i.g.

H and 50 C. Moderate stirring was used. The hydrogenation was stoppedafter 1.65 moles or 85% of the theoretical hydrogen needed to saturateall the aromatic rings was absorbed. The catalyst was removed byfiltration under N and g. of product; a thick light yellow liquid wasrecovered as bottoms by vac distilling off the dioxane. It had an epoxyvalue of 0.513 eq./100 g. or 91.5% of the original value 0.560 eq./100g. An infrared analysis using the 6.2 microns absorption band as areference confirmed the 85 hydrogen absorption measured.

These hydrogenated products can be obtained as aromatics completelyconverted to cycloaliphatics as a mixture of aromatic and cycloaliphaticgroups, depending on how much H is used. It may be a distinct advantagein some applications to only partially hydrogenate the aromatic groups.

11% by Weight of diethylene diamine added to a portion of this productconverted it into a hard tough infusible resin on standing overnight atroom temperature.

Example IV This experiment was run so. that the partially hydrogenatedproduct could be studied in surface coating applications.

parts of diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane wasdissolved in 1000 parts of purified dioxane and under a N blanketcharged to a stainless steel autoclave equipped for stirring. 12.5 partsof a finely divided catalyst comprising 10% rhodium or carbonapproximately 800-1200 mesh was added, the N replaced with hydrogen andthe pressure raised to 100 p.s.i.g. and the temperature to 50 C. Thehydrogenation, with stirring was run for one hour at which time 1.20moles of H had reacted. This calculates to 54% of the theoretical amountof H needed to hydrogenate all the aromatic rings to cycloaliphaticrings. The catalyst was filtered off in a N atmosphere and the productrecovered as 127 parts of bottoms by vac distilling oif the dioxane. Itwas a water white liquid having 8 poise viscosity and an epoxy value of0.552 eq./100 g. which is 94.0% of the starting value.

Example V A quantity of about 50% hydrogenated product having an epoxydiglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane value of 0.54eq./100 g. was milled on a three roll paint mill with commercial TiOuntil a fine dispersion and wetting was obtained. The resulting milledmixture contained 40% weight TiO 11% weight of diethylene triamine wasstirred in and with an .006 inch doctor blade tin panels were coated andcured 15 min. at 100 C.

The entire precedure above was repeated using the same batch ofdiglycidyl ether of 2,2-bis(4-hydroxyphenyl) propane which was nothydrogenated. Both sets of panels were masked /2 off with a foil and putin an Atlas Color Fade-O-Meter and periodically observed. Theunhydrogenated panels quickly developed a yellow color, particularly onthe uncovered half. After 20 hours the hydrogenated panels were left inbecause no visable change was observable. The exposure was continued 200hours at which time very little if any change in color, gloss orchalking developed. Thus, a very light resistant pigmented surfacecoating resulted from the partial hydrogenation of the diglycidyl etherof 2,2-bis(4-hydroxyphenyl) propane. Completely hydrogenated diglycidylether also has excellent resistance to light when formulated into asurface coating.

In a similar way coatings can be made by combining the hydrogenateddiglycidyl ether with urea-formaldehyde and melamine resins.

Example VI This example illustrates the advantage of having an inertsupport for the rhodium metal. The entire procedure and reagents wereduplicated as described in Example IV with the exception that thehydrogenation was not limited to a partial hydrogenation and thecatalyst was 21 parts of finely divided 5% rhodium on betaalumina having103 sq. meters per g. surface area. Samples were withdrawn during thehydrogenation so that the oxirane group could be measured. The belowtable illustrates that there was much less selectivity with thiscatalyst.

Moles H2 Consumed (percent of theory Oxirane Value of Solvent Free Time,hr. needed to Reaction Product, eq./l g.

hydrogcnate all aromatic groups) 2.5 .96 (43. 0.254 or 43.3% of originalvalue. 3.6 1.10 (50%) 0.104 or 23% of original value. 5.8. 2.63 (120%)0.000 or of original value.

An infrared analysis using the 6.2 micron band for reference showedcomplete hydrogenation of the aromatic ring.

Example VII This experiment was run in every way the same as Example IVwith the exceptions that the catalyst was 25 parts of 5% palladium oncarbon and the hydrogenation continued longer. After 4.75 hours 0.75mole (35% of that needed to hydrogenate the aromatic rings) of H hadreacted and the oxirane value dropped to 0.006 eq./ 100 g. of 1% of theoriginal value. An additional 1.5 hour of hydrogenation did not changethese values significantly.

Example VIII 125 parts of partially polymerized diglycidyl isophthalatewas dissolved in purified dioxane and charged under a blanket of N intoa stainless steel autoclave. 25 parts of a finely divided catalystcomprising 10% rhodium on carbon approximately 800-1200 mesh was added,the N replaced with H and hydrogenation proceeded at 50 C. and p.s.i.g.with moderate stirring. The hydrogenation was stopped when 1.0 mole of Hwas reacted or 77% of the calculated value to hydrogen the aromaticrings. Five samples taken during this period showed that the oxiranevalue did not drop below 91% of the original value.

The hydrogenated product of partially polymerized diglycidylisophthalate is a water white liquid having Gardner viscosity of 5 to 6.

Example X Part A. parts of diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane was dissolved in 1000 parts of purified dioxaneand charged under N into stainless steel stirred autoclave. 12.5 partsof a finely divided catalyst recovered from a previous run (10% rhodiumon carbon) was added, the N replaced with H and the H pressure broughtto 100 p.s.i.g. and heated to 50 C. With moderate stirring thehydrogenation was continued until no more H was taken up, this took 3hours. The product was recovered by filtering oil the catalyst under Nand the dioxane removed by vac flash distillation. A quantitativerecovery of water white product was obtained with an epoxy value of0.513 eq./100 g. or 87% of the original value. Infrared analysis usingthe 6.2 micron absorption as reference showed no aromatic groups.

Part B.The above experiment was repeated using 11.1 parts of thecatalyst recovered from Part A. In 5 hours, the hydrogen reactionstopped and the bottoms product, a water white liquid recovered. It hadan epoxy value of 0.526 eq./100 g. or 90.2% of the original value. Ithad a Gardner viscosity of 7 poise and showed no aromaticity whenanalyzed by infrared.

A tough casting having a Barcol hardness of 30-32 was obtained by mixingequal weights of the hydrogenated product with Nadic methyl anhydrideand .5% triphenyl phosphine, and heating for 2 hours.

The hydrogenated product has an unusually long pot life with amines, yetit gives a good hard strong casting when cured at room temperature. 6.99g. of hydrogenated diglycidyl ether was mixed with 0.79 g. of diethylenediamine and poured into an aluminum cup. It could be still easily pouredafter 8 hours and 45 minutes and became difiicult to pour after 10hours. When allowed to cure at room temperature overnight it was hard.After 48 hours, it had a Barcol hardness of 12 and was tough and waterwhite.

Example XI 25 parts of the glycidyl ester of 3,4-dihydro-2H-pyrane-2-carboxylate was dissolved in oxygen free purified dioxane and put intoa stainless steel stirred autoclave protected with an N blanket. 2 partsof a finely divided catalyst comprising 5% rhodium on carbonapproximately 800-1200 mesh, the N replaced with H and the H pressurebrought up to 50 p.s.i.g. and kept at room temperature. In one hour and30 minutes, 0.16 mole of hydrogen had reacted (95% of the calculatedamount necessary to saturate the pyrane ring). The reaction product wasfractionated and 22.5 parts of high boiling liquid recovered overhead.It showed no unsaturation by analysis and had an oxirane value of 0.48(89% of its original value).

Example XII 25 parts of a glycidyl polyether of2,2-bis(4-hydroxyphenyl)propane having a molecular weight of 900 and anepoxy value of 0.199 eq./100 g. (Polyether D in US. 2,633,458) wasdissolved in 420 parts of dioxane and charged under nitrogen into astainless steel stirred autoclave. 5 parts of a finely divided catalystmade up of 5% rhodium on carbon was added, and the nitrogen replacedwith hydrogen. The hydrogen pressure was brought to 100 p.s.i.g. and themixture heated to 50 C. With moderate stirring the hydrogenation wascontinued until no more hydrogen was taken up. This took 7 hours. The

Example XIII This example illustrates the preparation of cyclohexylglycidyl ether from phenyl glycidyl ether.

52 parts of phenyl glycidyl ether was dissolved in 415 parts ofisopropyl alcohol and the mixture charged under nitrogen into astainless steel autoclave. parts of a finely divided catalyst recoveredfrom a previous run rhodium on carbon) was .added, nitrogen replacedwith hydrogen and the hydrogen pressure brought to 100 p.s.i.g. andheated to 50 C. With moderate stirring the hydrogenation was continueduntil no more hydrogen was taken up, this took about 3 hours. Theproduct was recovered by filtering off the catalyst under nitrogen andthe dioxane removed by vacuum flash distillation. A Water white liquididentified as cyclohexyl glycidyl ether was recovered. The product had95% retention of the epoxide content and the aromatic content (6.3micron band) dropped below 5%. It had a pleasant odor in diluteconcentrations.

Example XIV 250 parts of purified dioxane was added to a glasshydrogenation vessel containing 25 parts of diglycidyl aniline. Fourparts of a finely divided catalyst (10% rhodium on carbon) was added,and after all the air was replaced with nitrogen, and the nitrogenreplaced with hydrogen, the hydrogen pressure was raised to 50 p.s.i.g.and shaking started and kept at room temperature.

After the theoretical amount of hydrogen had been consumed, the catalystwas removed by filtration under nitrogen and the dioxane removed byvacuum distillation. The remaining product was a liquid identified asN,N-diglycidyl aminocyclohexane.

The above product when heated at 100 C. with diethylene triamine, setsup to form a hard solid casting.

Example XV 410 parts of purified dioxane was added to the hydrogenationvessel containing 25 parts of a coploymer of allyl glycidyl ether andstyrene having a molecular weight of 780 and an epoxy value of 0.546eq./100 g. 5 parts of a finely divided catalyst (10% rhodium on carbon)was added, and after all the air was replaced with nitrogen, and thenitrogen replaced with hydrogen, the hydrogen pressure was raised to 50p.s.i.g. and shaking started and kept at room temperature.

After about 3 moles of hydrogen had been consumed, the catalyst wasremoved by filtration under nitrogen and the dioxane removed by vacuumdistillation. The remaining product was identified as a correspondingcopolymer of allyl glycidyl ether and vinyl cyclohexane. It had lessthan 5% of the original aromatic groups as estimated from its infraredsystems using the 6.2 micron band as referred.

The above product when heated at 100 C. with diethylene triamine sets upto form a hard solid casting.

Example XVI 250 parts of purified dioxane was added to the hydrogenationvessel containing 39 parts of epoxidized dicrotyl isophthalate having anepoxy value of 0.60 eq./100 g. 5 parts of the finely divided catalystmade up of 10% rhodium on carbon was added to the vessel, and after allthe air had been removed as in the preceding examples, hydrogen wasintroduced under pressure of 50 p.s.i.g. and the vessel shaking at roomtemperature.

After about 0.40 mole of hydrogen had been consumed, the catalyst wasremoved by filtration under nitrogen and 14 the dioxane removed byvacuum distillation. The remaining product was identified as epoxidizeddicrotyl cyclohexanedicarboxylate.

The above product when heated at C. with diethylene triamine sets up toform a hard solid casting.

Example XVII The preceding example was repeated with the exception thatthe polyepoxide employed was epoxidized dimethallyl isophthalate. Theproduct obtained in this case was identified as epoxidized dimethallylcyclohexanedicarboxylate. The resulting product can be cured withdiethylene triamine to form hard insoluble castings.

Example XVIII 250 parts of the purified dioxane was added to thehydrogenation vessel containing 52 parts of glycidyl ether ester ofdiphenolic acid. 5 parts of a finely divided catalyst made up of 10%rhodium on carbon approximately- Example XIX The preceding example wasrepeated with the exception that the unsaturated epoxy compound isglycidyl ether of Z-glycidylphenol. The resulting product is a whiteliquid having an epoxy value of .456 eq./100 g.

Example XX 400 parts of dioxane, purified by refluxing over caustic,distilling. and keeping covered with pure N was charged into a stainlesssteel autoclave containing 52 parts of diglycidyl ether of2,2-bis'(4-hydroxyphenyl) propane which was also protected with pure NWhen the solution was complete 50 parts of a catalyst was added thatconsisted of 0.8 6% rhodium on powdered alpha-alumina. This catalyst hada surface area of 13 sq. meters/gram as measured by N absorption. X-raymeasurements showed the support to be predominantly alpha-alumina.

The vessel was flushed with pure N and then the N replaced with H; andthe pressure brought up to 380 p.s.i. at 25 C. and stirring started.After about 3 hours at 25 C. and 20 hours at 50 C. .99 moles of H wasabsorbed and the reaction stopped. The catalyst was filtered off andExample XXI The above example was repeated using catalyst (0.86% rhodiumon alpha-alumina) recovered from previous hydrogenations. Thehydrogenation was run for 2.25 hrs. at 100 to 420 p.s.i. and 35-70 C.When the product was worked up spectroscopic analysis, using the 6.2micro band for reference, showed complete hydrogenation of the aromaticrings. The oxirane content (analyzed by reaction with HCl) of the waterwhite product was 93% of the original value. This example shows how thecatalyst irnproves in rate and selectivity after a preconditioning.

The catalyst preconditioning can be done in part by treating thecatalyst for several hours under pressure of hydrogen with or withoutthe use of solvent and elevated temperatures.

I claim as my invention:

1. A process for preparing new epoxy compounds which comprises treatingan organic compound possess- 15 ing at least one Vic-epoxy group and atleast one carbonto-carbon double bond unsaturation with hydrogen in thepresence of a finely-divided catalyst containing a metal of the groupconsisting of rhodium and ruthenium at a temperature below about 150 C.

2. A process for preparing substantially saturated epoxy compounds whichcomprises reacting an organic compound possessing at least one vie-epoxygroup and at least one carbon-to-carbon double bond unsaturation withhydrogen in the presence of a rhodium-containing catalyst supported onan inert carrier, said carrier being inert toward the reaction withepoxide compound and also being inert toward epoxide rings when in thepresence of the catalyst, at a temperature below 150 C.

3. A process as in claim 2 wherein the catalyst is rhodium metalsupported on carbon.

4. A process as in claim 2 wherein the catalyst is rhodium metalsupported on alpha-alumina.

5. A process as in claim 2 wherein the hydrogenation is conducted at atemperature between 15 C. and 150 C. and at a hydrogen pressure ofp.s.i.g. to 1000 p.s.i.g.

6. A process as in claim 2 wherein the catalyst is a rhodiummetal-rhodium oxide mixture supported on carbon.

7. A process as in claim 2 wherein the unsaturated epoxy compound is anepoxy ether of a polyhydric phenol.

8. A process as in claim 2 wherein the unsaturated epoxy compound is anepoxy ester of an aromatic polycarboxylic acid.

9. A process as in claim 2 wherein the unsaturated epoxy compound is anepoxyalkyl-substituted aromatic compound wherein the epoxyalkyl group isattached to the ring through carbon.

10. A process as in claim 2 wherein the unsaturated epoxy compound is aN epoxy substituted aromatic amine.

11. A process as in claim 2 wherein the unsaturated epoxy compound is apolymer of an alkenyl epoxyalkyl ether and an aromatic unsaturatedcompound.

12. A process as in claim 2 wherein the inert carrier is finely-dividedcarbon.

13. A process as in claim 2 wherein the unsaturated epoxy compound is apolymer of an ester of an epoxyalkanol and a carboxylic acid and anaromatic unsaturated compound.

14. A process as in claim 2 wherein the unsaturated epoxy compound is aglycidyl ether of 2,2-bis (4-hydroxypheny1)propane.

15. A process as in claim 2 wherein the unsaturated epoxy compound is acopolyrner of allyl glycidyl ether and styrene.

16. A process as in claim 2 wherein the unsaturated epoxy compound is aglycidyl ester of an aromatic polycarboxylic acid.

17. A process as in claim 2 wherein the unsaturated epoxy compound isphenyl glycidyl ether.

18. A process as in claim 2 wherein the unsaturated epoxy compound is aglycidyl ether of a phenol-formaldehyde condensate.

19. A process as in claim 2 wherein the unsaturated epoxy compound is apartially epoxidized polybutadiene.

20. A process as in claim 2 wherein the unsaturated epoxy compound isdiepoxyethylbenzene.

21. A process for preparing substantially saturated epoxy compoundswhich comprises reacting an organic compound possessing at least oneVic-epoxy group and at least one carbon-to-carbon unsaturation withhydrogen in the presence of a rhodium metal supported on an inertcarrier, said carrier being inert toward the reaction with epoxycompounds and also being inert toward epoxy compounds in the presence ofthe aforementioned catalyst, at a temperature below C.

22. A process as in claim 21 wherein the catalyst is rhodium metalsupported on alpha-alumina.

No references cited.

WILLIAM H. SHORT, Primary Examiner.

T. PERTILLA, Assistant Examinen

1. A PROCESS FOR PREPARING NEW EPOXY COMPOUNDS WHICH COMPRISES TREATINGAN ORGANIC COMPOUND POSSESSING AT LEAST ONE VIC-EPOXY GROUP AND AT LEASTONE CARBONTO-CARBON DOUBLE BOND UNSATURATION WITH HYDROGEN IN THEPRESENCE OF A FINELY-DIVIDED CATALYST CONTAINING A METAL OF THE GROUPCONSISTING OF RHODIUM AND RUTHENIUM AT A TEMPERTURE BELOW ABOUT 150*C.